Thermodynamic modeling of REE behavior in oxidized hydrothermal fluids of high sulfate sulfur concentrations

Thermodynamic calculations using the HCh software were made for mineral equilibriums including REEs in the fluoride–sulfide–chloride–carbonate–sulfate–system in the presence of Na, Ca, and P with fluids of various acidities–alkalinities [11]. The obtained thermodynamic characteristics of thenardite allowed us to carry out the calculations for this phase under complicated hydrothermal conditions simulating the presence of oxidized fluids at 500–100°C and 2000–125 bar. Among other solid phases, REEs–fluorite, monazite, and REE–F–apatite were formed as CaF₂–(Ln,Y)F₃, LnPO₄, and Ca₅(PO₄)₃F–(Ln,Y)₃(PO₄)₃ ideal solid solutions, respectively, where Ln is La, Ce, Pr, Nd, Sm, Eu, and Gd. Xenotime, anhydrite, elemental sulfur, and calcite were found as well.     

Typochemical features of the rare-earth component of monazites from the Ilmen’ reserve

By means of X-ray fluorescence with synchroton radiation (XRF-SR), the contents of all 14 rare-earth elements (REEs) and that of Y were determined in 12 monazite samples from different veins in the Ilmen’ Reserve (South Urals). It was found that, in anphibole-micaceous-carbonate mineralized zones within metabasites, monazites were pronouncedly depleted in middle and, especially, in heavy rare-earth elements (HREEs) (from 0.25% and below for Sm, 0.08% or below for Gd, 0.03% for Dy, 0.01% for Er and Tm, below 0.005% for Yb, trace amounts of other odd HREEs, at a Y content of 0.1% or below). Monazites from the veins of granitic pegmatites were characterized by vastly decreased La contents (4–8 compared to 11–13% for the group above), at high values for Pr (to 3%), Nd (to 8%), Sm (to 1.3%), Gd (to 1.1%), Dy (to 0.9%), Er (to 0.2%), Yb (to 0.05%), and Y (from 0.2 to 1.7%). Here, the values for odd REEs are also quite high compared to the group above (to 0.2% for Tb, to 0.08% for Ho, and to 0.1% for Tm).

     

Geochemical mobility of Au and Ag during hydrothermal transfer and precipitation: Thermodynamic simulation

The thermodynamic simulation of the geochemical mobility of Au and Ag during their hydrothermal transfer and precipitation was conducted with regard for the formation of continuous nonideal Au-Ag solid solutions (or Au_XAg_1?X) alloys) and with the analysis of the effects of principal physicochemical parameters (temperature, pH, redox potential, and the concentrations of sulfide sulfur and chloride ions) on the solubility of Au-Ag alloys of various composition. Predominant Au and Ag complexes and the types of solutions were identified, which are characterized by different extractive ability with respect to these metals. A tendency in the variations in the Au/Ag ratio in the solid phase during the evolution of the hydrothermal process was revealed with regard for various conditions under which Ag sulfides can occur. The possible effect of the Au_XAg_1?X/solution ratio on the composition of the Au-Ag mineralization was demonstrated, and tendencies in the variations in the composition (fineness) of the alloys during their redeposition were identified.